A hybrid plasma catalytic system consisting of a dielectric barrier discharge (DBD) reactor and relaxor ferroelectrics is investigated for syngas generation via the carbon dioxide reforming of methane. The study tests three kinds of packing materials, including two relaxor ferroelectrics BaZr0.75T0.25O3 (BZT; εr = 149), BaFe0.5Nb0.5O3 (BFN; εr = 2025), and glass beads (εr = 3-5). The BFN and BZT packed-bed DBD reactors achieve higher CO2 and CH4 conversions and better energy efficiencies for syngas production than the DBD. On the contrary, the DBD packed with glass beads achieves lower conversions and energy efficiencies than the DBD. In terms of packings filled in a DBD reactor, there is a trade-off between an enhancement of the electric field strength and a reduction of the gas retention time. It is interesting that the conversions are increased with the increase of the dielectric constant of the packings tested in the study. Overall, a relaxor ferroelectric with a high dielectric constant is a good candidate for constituting the packed-bed DBDs. The finding is beneficial to further development of a plasma-based technique for the dry reforming of methane (DRM).